Nitrocellulose propellant composition containing metal and triaminoguanidinium hydrazinium diazide

ABSTRACT

The present invention comprises a solid double-base propellant composition having on a weight basis from about 2 to about 23 percent of a light metal fuel, from about 14 to about 35 percent of a particulate solid oxidizer, from about 12 to about 35 percent triaminoguanidinium hydrazinium diazide and from about 30 to about 50 percent of a plasticized nitrocellulose binder.

llnited States Patent 1 1 Flynn et a1.

[ NITROCELLULOSE PROPELLANT COMPOSITION CONTAINING METAL AND TRlAMlNOGUANlDlNlUM HYDRAZlNlUM DIAZIDE [75] lnventors: James P. Flynn; George A. Lane;

John J. Plomer, all of Midland,

Mich.

[73] Assignee: The Dow Chemical Company,

Midland, Mich.

[22] Filed: June 16, 1965 [21] Appl. No.: 465,253

[52] U.S. Cl l49/l9.4, 149/198, 149/20,

149/22, 149/36, 149/38 [51] Int. Cl C06d 5/06 [58] Field of Search 149/18, 19, 20, 38, 44,

[451 Feb. 11,1975

[56] References Cited UNITED STATES PATENTS 3,053,709 9/1962 Herty 149/198 3,138,499 6/1964 Camp et a1. 149/198 Primary ExaminerBenjamin R. Padgett Attorney, Agent, or FirmC. Kenneth Bjork [57] ABSTRACT 5 Claims, No Drawings N ITROCELLULOSE PROPELLANT COMPOSITION CONTAINING METAL AND TRIAMINOGUANIDINIUM I-IYDRAZINIUM DIAZIDE This invention relates to propellants and more particularly is concerned with a novel solid double base propellant composition exhibiting a high specific impulse.

It is a principal object of the present invention to provide a novel high energy propellant composition exhibiting a high specific impulse.

It is another object of the present invention to provide a novel double base solid propellant composition that cures at room temperature to a rubbery elastomer without undesirable gas formation.

- toluene diisocyanate.

These and other objects and advantages readily will become apparent from the detailed description presented hereinafter.

The present invention comprises a solid double-base propellant composition containing from about 2 to about 23 weight percent of a particulated solid fuel, from about l4 to about 35 weight percent of a particulated solid oxidizer, from about l2 to about 35 weight percent triaminoguanidinium hydrazinium diazide and from about 30 to about 50 weight percent of a binder.

Ordinarily, the composition comprises from about 8 to about 23 weight percent of a particulated solid fuel, from about 14 to about 35 weight percent ofa particulated solid oxidizer, from about 12 to about 35 weight percent triaminoguanidinium hydrazinium diazide and from about 30 to about 40 weight percent of a plasticized nitrocellulose binder.

Ordinarily the fuel is a member selected from the group consisting of aluminum, beryllium, boron and mixtures thereof.

The oxidizer employed in the composition usually is selected from the group consisting of ammonium perchlorate, ammonium nitrate, hydrazine nitroformate, nitronium perchlorate, cyclotrimethylenetrinitramine, cyclotetramethylenetetranitramine and mixtures thereof.

Preferably, as indicated hereinbefore, plasticized nitrocellulose is used as the binder. Ordinarily the binder is a blend containing, on a weight basis, from about 1 to about 5 parts ofa nitroplasticizer to 1 part ofa plastisol grade nitrocellulose. Diethyleneglycol dinitrate,

triethyleneglycol dinitrate, trimethylolethane trinitrate and mixtures thereof are particularly effective plasticizers.

One preferred embodiment of the present novel double base propellant composition consists essentially of from about 15 to about weight percent aluminum, from about l7 to about 26 weight percent ammonium perchlorate, from about 18 to about 23 weight percent triaminoguanidinium hydrazinium diazide and. from about to about weight percent of a plasticized nitrocellulose binder consisting of about 25 parts by weight plastisol grade nitrocellulose, 55 to 60parts by weight trimethylolethane trinitrate, 15 parts by weight A second preferred embodiment of the present invention consists essentially of on a weight basis from about 9 to about 13 percent beryllium, from about 23 to about 27 percent ammonium perchlorate, about 24 percent triaminoguanidinium hydrazinium diazide and about 40 percent of the plasticized nitrocellulose binder of composition as described hereinbefore.

The present propellants usually are fabricated by mixing and blending the fuel, oxidizer and triaminoguanidinium hydrazine azide into the plasticized nitrocellulose binder, i.e., nitrosol binder. After mixing to provide a substantially homogeneous blend, the formulation is cast, extruded or otherwise formed and cured to produce a solid, elastomeric propellant grain of predetermined configuration.

Satisfactory propellant grains are produced by curing the grains at room temperature, i.e. from about l8 to about 25 C., for about 12 to 24 hours, ordinarily about 16 hours with the less energetic nitroplasticizers. e.g., triethyleneglycol dinitrate or a mixture of trimethylolethane trinitrate and triethylene glycol dinitrate. With the more energetic plasticizers, e.g., trimethylolethane trinitrate alone, preferably higher curing temperatures of from about 50 to about 60 C. are used. At these temperatures undesirable gases may be liberated during this curing period. This gassing at the higher curing temperatures can be avoided by incorporating from about l to 2 percent by weight of a diisocyanate or an isocyanate into the propellant composition.

The present composition having triaminoguanidinium hydrazinium diazide as an essential component has a specific impulse markedly increased over the corresponding double base system not employing this component. The present novel composition finds utility as a propellant for rockets and rocket driven missiles.

If the metal fuel member is not included, the present composition exhibits a somewhat reduced specific impulse but finds a particularly effective utility as a gas generator solid propellant or a smokeless solid propellant.

The following Examples will serve to further illustrate the present invention but are not meant to limit it thereto.

EXAMPLE 1 A number of propellant grains were formed by blending finely divided aluminum or beryllium, ammonium perchlorate, triaminoguanidinium hydrazinium diazide and a nitrosol binder. The solid components ranged in particle size from about 40 to about mesh, US. Standard Sieve. Each of the blends was cast into a pro pellant' grain, cured, and fired in a closed bomb. The heat energy liberated and actual specific impulse were determined for each grain. The efficiency of each grain was determined by comparing the observed specific impulse with that theoretically calculated for the composition. Table I, which follows, summarizes the data and results of this study.

Table I Propellant Composition Combustion Results Nitrosol" Al Be AP THA AH Isp obs.) lsp (theo) Eff. Run No. by weight) (cal/g.) (sec.) (sec.) (71) l 40" I9 17 24 I387 247 274.8 89.8 2 40" 16 26 18 1543fl 247 272.6 90.6

Table I -Continued Propellant Composition Combustion Results Nitrosol" Al Be AP THA AH lsp (obs) lsp (theo) Eff.

Run No. by weight) (cal/g.) (sec.) (sec.) (7() 3 35" 16 26 23 ISOOfl 243 273.9 88.7

"' 25 parts by weight plasticized grade nitrocellulose, 55 parts by weight trimethylolethane trinitrate, parts by weight diethyleneglycol dinitrate. 5 parts by weight toluene diisocyanate.

25 parts by weight plastisol grade nitrocellulose, 60 parts by weight lrimethylolethane trinitrate and 15 parts by weight triethylene glycol dinitrate. ammonium perchlorate triaminoguanidinium hydrazine diazide EXAMPLE 2,

lulose, 26 parts by weight trimethylolethane trinitrate and 2 parts by weight toluene diisocyanate were blended together to form a plasticized nitrocellulose binder. About 19 parts by weight aluminum and 21 parts by weight triaminoguanidinium hydrazinium diazide were mixed into the binder followed by about parts by weight ammonium perchlorate. All solids ranged from about 40 to about 100 mesh U.S. Standard Sieve in particle size. The resulting blend was mixed until a substantially homogeneous mass resulted. The formulation was cast and cured for about 16 hours at a temperature ranging from about 50 to about 60 C. The resulting propellant grain was substantially voidfree and had a density of about 1.7 grams per cubic centimeter.

When fired in a rocket motor, this grain burned smoothly to completion.

EXAMPLE 3 A number 01 formulations of the present invention \vcrc fabricated into rocket grains. The combustion temperature and theoretical impulse of each of the resultant propellants were calculated. The propellant formulations data and performance results from this study are presented in Table 11 which follows.

In a manner similar to that described for the preceding Examples, propellants having boron and mixtures of aluminum and/or beryllium with boron as a fuel and ammonium nitrate and nitronium perchlorate as an oxidizer plus triaminoguanidinium hydrazinium azide and mulated. Further, it is to be understood that the fuel and oxidizer components listed hereinbefore can be utilized in various combinations in the present propellants.

Various modifications can be made in the present invention without departing from the spirit or scope thereof for it is understood that we limit ourselves only as defined in the appended claims.

We claim:

1. A solid double base propellant composition comprising on a weight basis a. from about 2 to about 23 percent of a particulated solid fuel member selected from the group consisting of aluminum, beryllium, boron and mixtures thereof,

b. from about 14 to about 35 percent of a particulated solid oxidizer selected from the group consisting of ammonium perchlorate, ammonium nitrate, hydrazine nitroformate, nitronium perchlorate, cyclotrimethylenetrinitramine, cyclotetramethylenetetranitraminc and mixtures thereof,

from about 12 to about 35 percent triaminoguanidinium hydrazinium diazide, and

d. from about 30 to about percent of a plasticized nitrocellulose binder. 2. A solid double base propellant composition consisting essentially of on a weight basis a. from about 8 to about 23 percent of a member se- Propellant Composition Results NC TMETN Al Be THA AP HNF Combustion Temp. Specific impulse Run No. wt. percent ('14) lsp. (sec.)

"' Nitrocellulose Trimethylolethane trinitrate 'l'riaminoguanidiniuni hydrazinium dia'lide Ammonium perchlorate Hydra/inc Nitrut'mniatc b. from about 14 to about 35 percent of a member selected from the group consisting of particulated ammonium perchlorate and hydrazine nitroformate,

c. from about 12 to about 35 percent triaminoguanidinium hydrazinium diazide, and

d. from about 30 to about 40 percent of a plasticized nitrocellulose binder, said binder consisting of from about 16 to about 40 weight percent plastisol grade nitrocellulose and from about 84 to about 60 weight percent of a member selected from the group consisting of trimethylolethane trinitrate, diethyleneglycol dinitrate, triethyleneglycol dinitrate and mixtures thereof.

3. A solid double base propellant composition consisting essentially of on a weight basis a. from about to about percent particulate aluminum,

b. from about 17 to about 26 percent particulate ammonium perchlorate,

c. from about 18 to about 23 percent triaminoguanidinium hydrazinium diazide, and

d. from about to about percent of a plasticized nitrocellulose binder consisting of about 25 parts by weight plastisol grade nitrocellulose, about 55 to about 60 parts by weight trimethylolethane trinitrate, 15 parts by weight triethyleneglycol dinitrate and 0 to about 5 parts by weight toluene diisocyanate.

4. A solid double base propellant composition consisting essentially of on a weight basis a. from about 9 to about 13 percent particulate beryllium,

b. from about 23 to about 27 percent particulate ammonium perchlorate,

c. about 24 percent triaminoguanidinium hydrazinium diazide, and

(1. about 40 percent of a plasticized nitrocellulose binder consisting of about 25 parts by weight plastisol grade nitrocellulose, about 55 to about parts by weight trimethylolethane trinitrate, l5 parts by weight triethyleneglycol dinitrate and 0 to about 5 parts by weight toluene diisocyanate.

5. A solid double base propellant composition consisting essentially of on a weight basis a. about 19 percent particulate aluminum,

b. about 20 percent particulate ammonium perchlorate,

c. about 21 percent triaminoguanidinium hydrazinium diazide, and

d. about 40 percent of a plasticized nitrocellulose binder, said binder consisting; of about 30 weight percent plastisol grade nitrocellulose, about weight percent trimethylolethane trinitrate and about 5 weight percent toluene diisocyanate.

l l l 

1. A SOLID DOUBLE BASE PROPELLANT COMPOSITION COMPRISING ON A WEIGHT BASIS A. FROM ABOUT 2 TO ABOUT 23 PERCENT OF A PARTICULATED SOLID FUEL MEMBER SELECTED FROM THE GROUP CONSISTING OF ALUMINUM, BERYLLIUM, BORON AND MIXTUES THEREOF, B. FROM ABOUT 14 TO ABOUT 35 PERCENT OF A PARTICULATED SOLID OXIDIZER SELECTED FROM THE GROUP CONSISTING OF AMMONIUM PERCHLORATE, AMMONIUM NITRATE, HYDRAXINE NITROFORMATE, NITRONIUM PERCHLORATE, CYCLOTRIMETHYLETRINITRAMINE, CYCLOTETRAMETHYLENETETRANITRAMINE AND MIXTURES THEREOF, C. FROM ABOUT 12 TO ABOUT 35 PERCENT TRIAMINOGUANIDINIUM HYDRAZINIUM DIAZIDE, AND D. FROM ABOUT 30 TO ABOUT 50 PERCENT OF A PLASTICIZED NITROCELLULOSE BINDER.
 2. A solid double base propellant composition consisting essentially of on a weight basis a. from about 8 to about 23 percent of a member selected from the group consisting of particulated aluminum and beryllium, b. from about 14 to about 35 percent of a member selected from the group consisting of particulated ammonium perchlorate and hydrazine nitroformate, c. from about 12 to about 35 percent triaminoguanidinium hydrazinium diazide, and d. from about 30 to about 40 percent of a plasticized nitrocellulose binder, said binder consisting of from about 16 to about 40 weight percent plastisol grade nitrocellulose and from about 84 to about 60 weight percent of a member selected from the group consisting of trimethylolethane trinitrate, diethyleneglycol dinitrate, triethyleneglycol dinitrate and mixtures thereof.
 3. A solid double base propellant composition consisting essentially of on a weight basis a. from about 15 to about 20 percent particulate aluminum, b. from about 17 to about 26 percent particulate ammonium perchlorate, c. from about 18 to about 23 percent triaminoguanidinium hydrazinium diazide, and d. from about 35 to about 40 percent of a plasticized nitrocellulose binder consisting of about 25 parts by weight plastisol grade nitrocellulose, about 55 to about 60 parts by weight trimethylolethane trinitrate, 15 parts by weight triethyleneglycol dinitrate and 0 to about 5 parts by weight toluene diisocyanate.
 4. A solid double base propellant composition consisting essentially of on a weight basis a. from about 9 to about 13 percent particulate beryllium, b. from about 23 to about 27 percent particulate ammonium perchlorate, c. about 24 percent triaminoguanidinium hydrazinium diazide, and d. about 40 percent of a plasticized nitrocellulose binder consisting of about 25 parts by weight plastisol grade nitrocellulose, about 55 to about 60 parts by weight trimethylolethane trinitrate, 15 parts by weight triethyleneglycol dinitrate and 0 to about 5 parts by weight toluene diisocyanate.
 5. A solid double base propellant composition consisting essentially of on a weight basis a. about 19 percent particulate aluminum, b. about 20 percent particulate ammonium perchlorate, c. about 21 percent triaminoguanidinium hydrazinium diazide, and d. about 40 percent of a plasticized nitrocellulose binder, said binder consisting of about 30 weight percent plastisol grade nitrocellulose, about 65 weight percent trimethylolethane trinitrate and about 5 weight percent toluene diisocyanate. 